Experimental Reversal of the Na-K Exchange Reaction Between Muscovite-Paragonite Crystalline Solutions and a 2 Molal Aqueous (Na,K)Cl Fluid

Single-phase 2M₁ muscovite-paragonite crystalline solutionsin the range 0?00–0?10 and 0?70–1?00 X_ms have beensynthesized by hydrothermal treatment of gels of appropriatecompositions at 600–700?C, and 7 to 18 kb P_H2O. The molarvolumes of these micas may be expressed as V(J/b?mol) = 13?1845+1?463X_ms+0?0160 X_ms²–0?1679 X_ms³ (?0?005), which translateto a substantial positive excess molar volume of mixing. Na-K ion exchange experiments between presynthesized 2M₁ micacrystalline solutions and 2 molal aqueous (Na,K)Cl fluids failedto proceed to completion despite 98 day runs at 500–600?C,6 kb P_total. Results of analogous exchange experiments provedencouraging however, when a much finer-grained 1M mica was usedas starting material. Applying the tie line rotation technique,reversal of ion exchange experiments could be achieved in the2-phase fields, not, however, in the 3-phase field of the ms-pg-NaCl-KClreciprocal ternary. Using gels as starting material, reversalexperiments were eventually successful both in the 2-phase andthe 3-phase fields; the results of reversal experiments withinthe two-phase fields being identical to those obtained earlierusing 1M micas. Four isobaric-isothermal sections through the ms-pg-NaCl-KClternary were reversibly determined at 450?C/5 kb, 550?C/6 kb,550?C/15 kb, and 620?C/7 kb. At 450?C, the coexisting mica compositionsin the 3-phase field (2 micas plus 1 fluid) are 0?10 and 0?77X_ms, at 550?C they are 0?10 and 0?60 X_ms, and finally, at 620?Cthese are 0?12 and 0?51 X_ms. To the extent that internal equilibriumwas accomplished between the coexisting micas, these data wouldindicate a wide solvus at 450?C, narrowing gradually with increasingtemperature to 620?C. The critical temperature will be wellin excess of 620?C, although the mica at the critical conditionwill prove to be metastable with respect to the assemblage alkalifeldspars+corundum+H₂O. The companion paper by Chatterjee & Flux (1986) presentsa thermodynamic analysis of the above experimental data.     

Phase Equilibria in the Pyroxene Quadrilateral

Experimental phase equilibrium data on compositions of coexistingpyroxenes in the quadrilateral enstatite-diopside-ferrosilite-hedenbergitehave been used to model pyroxene solid solutions and to formulatepyroxene geothermometers. Each pyroxene is treated as a solidsolution of four quad-components using the Kohler formulation where G_ij^* is the excess free energy of mixing in a binary solutioncalculated with binary mole fractions (e.g. X_i^o = X_i/(X_i+X_j))and X_i is the mole fraction in a multicomponent solution. Thefit to the experimental data is achieved by minimizing the totalGibbs free energy of the assemblage. The following set of thermochemicaldata and simple mixture parameters (W_ij) are found to be bestsuited. Standard (T = 298?15 K) enthalpy and entropy of formationfrom elements for fictive orthohedenbergite are –1416?8kJ and 84?88 J K^–1 mol ^–1 respectively. The heatcapacity is given by 114?67+17?09E-3T–31?40E5T^–2.The W_ij data are: Opx: W₁₂ = W₂₁ = 25 W₁₃ = (13?1–0-015T),W₃₁ = (3?37–0?005T), W₂₃ = 20, W₃₂ = 16, W₂₄ = 5, W₄₂= 7, W₃₄ = 15, W₄₃ = 15; Cpx: W₁₂ = (25?484+0?0812P), W₂₁ =(31?216–0?0061P),W₃₁ = W₁₃ = 0W₁₄ = (93?3–0?045T), W₄₁ = (–20?0+0?028T),W₂₃ = 24, W₃₂ = 15, W₂₄ = 12, W₄₂ = 12, W₃₄ = (16?941+0?00592P),W₄₃ = (20?697–0?00235P). Coexisting pyroxene compositionshave been computed in the temperature range of 700 to 1400?C. Two geothermometers have been constructed, one based on atomicfraction of iron (Fe/(Fe + Mg)) in orthopyroxene and the Fe-Mgdistribution coefficient and the other, based on wollastonitecontent of clinopyroxene. The two scales yield different temperatureswhen applied to the same rock. In igneous pyroxenes, the Catransfer ceased at 150 to 200?C above the closure temperatureof the Fe-Mg ion-exchange. In metamorphic rocks an oppositeeffect seems to have prevailed.     

Petrology of Biotite-Cordierite-Garnet Gneiss of the McCullough Range, Nevada I. Evidence for Proterozoic Low-Pressure Fluid-Absent Granulite Grade Metamorphism in the Southern Cordillera

Proterozoic migmatitic paragneisses exposed in the McCulloughRange, southern Nevada, consist of cordierite+almanditic garnet+biotite+sillimanite+plagioclase+K-feldspar+quartz+ilmenite+hercynite.This assemblage is indicative of a low-pressure fades seriesat hornblende-granulite grade. Textures record a single metamorphicevent involving crystallization of cordierite at the expenseof biotite and sillimanite. Thermobarometry utilizing cation exchange between garnet, biotite,cordierite, hercynite, and plagioclase yields a preferred temperaturerange of 590–750?C and a pressure range of 3–4 kb.Equilibrium among biotite, sillimanite, quartz, garnet, andK-feldspar records a_H2O between 0?03 and 0?26. The low a_H2Otogetherwith low f_O2 (QFM) and optical properties of cordierite indicatemetamorphism under fluid-absent conditions. Preserved mineralcompositions are not consistent with equilibrium with a meltphase. Earlier limited partial melting was apparently extensiveenough to cause desiccation of the pelitic assemblage. The relatively low pressures attending high-grade metamorphismof the McCullough Range paragneisses allies this terrane withbiotite-cordierite-garnet granulites in other orogenic belts.aosure pressures and temperatures require a transient apparentthermal gradient ofat least 50?C/km during part of this Proterozoicevent in the southern Cordillera. ^*Present address: Institute of Geophysics and Planetary Physics, University of California, Los Angeles, CA 90024-1567     

The Synthesis and Stability of Anthophyllite

The pure magnesium orthorhombic amphibole, anthophyllite, hasbeen synthesized and its upper and lower stability limits havebeen established by reversible hydrothermal experiments. Thesynthetic mineral has refractive indices n_x=1?587?0?001, n_y=1?602?0?005,n_z=1?613?0?001, and unit-cell dimensions of a₀=18?61?0?02 ?,b₀=18?01?0?06 ?, c₀=5?24?0?01 ?. The mineral is stable overa narrow temperature range in the presence of the phase H₂O.At a P_H2O of 1,000 bars the upper stability limit is 745??10?C and the lower stability limit is 667??8? C. Rate studies indicate that anthophyllite can nucleate at temperaturesabove its upper stability limit by disintegration of talc sheetsinto strips of double chains. The activation energy for thisprocess is 150?30 kcal mol^–1. Application of the data to rocks of the Balmat area, New York,suggests that the equilibrium pressure of water during the metamorphismwas significantly less than the total pressure. The data indicatethat monomineralic zones of anthophyllite in ultramafic rocksare due to the presence of a steep gradient in the activityof H₂O, or a steep gradient in temperature, or both, acrossthe zones.     

The Substitution of Al and F in Titanite at High Pressure and Temperature: Experimental Constraints on Phase Relations and Solid Solution Properties

Experimental studies were carried out to evaluate phase relationsinvolving titanite–F–Al-titanite solid solutionin the system CaSiO₃–Al₂SiO₅–TiO₂–CaF₂. Theexperiments were conducted at 900–1000°C and 1·1–4·0GPa. The average F/Al ratio in titanite solid solution in theexperimental run products is 1·01 ± 0·06,and X_Al ranges from 0·33 ± 0·02 to 0·91± 0·05, consistent with the substitution [TiO²⁺]_–1[AlF²⁺]₁.Analysis of the phase relations indicates that titanite solidsolutions coexisting with rutile are always low in X_Al, whereasthe maximum X_Al of titanite solid solution occurs with fluoriteand either anorthite or Al₂SiO₅. Reaction displacement experimentswere performed by adding fluorite to the assemblage anorthite+ rutile = titanite + kyanite. The reaction shifts from 1·60GPa to 1·15 ± 0·05 GPa at 900°C, from1·79 GPa to 1·375 ± 0·025 GPa at1000°C, and from 1·98 GPa to 1·575 ±0·025 GPa at 1100°C. The data show that the activityof CaTiSiO₄O is very close to the ideal molecular activity model(X_Ti) at 1100°C, but shows a negative deviation at 1000°Cand 900°C. The results constrain     

Melting of a Hydrous Mantle: I. Phase Relations of Natural Peridotite at High Pressures and Temperatures with Controlled Activities of Water, Carbon Dioxide, and Hydrogen

Four natural peridotite nodules ranging from chemically depletedto Fe-rich, alkaline and calcic (SiO₂ = 43.7–45.7 wt.per cent, A1₂O₃ = 1.6O–8.21 wt. per cent, CaO = 0.70–8.12wt. per cent, alk = 0.10–0.90 wt. per cent and Mg/(Mg+Fe²⁺)= 0.94–0.85) have been investigated in the hypersolidusregion from 800? to 1250?C with variable activities of H₂O,CO₂, and H₂. The vapor-saturated peridotite solidi are 50–200?Cbelow those previously published. The temperature of the beginningof melting of peridotite decreases markedly with decreasingMg/(Mg+SFe) of the starting material at constant CaO/Al₂O₃.Conversely, lowering CaO/Al₂O₃ reduces the temperature at constantMg/(Mg+Fe) of the starting material. Temperature differencesbetween the solidi up to 200?C are observed. All solidi displaya temperature minimum reflecting the appearance of garnet. Thisminimum shifts to lower pressure with decreasing Mg/(Mg + Fe)of the starting material. The temperature of the beginning ofmelting decreases isobarically as approximately a linear functionof the mol fraction of H₂O in the vapor (X_H2O^v). The data alsoshow that some CO₂ may dissolve in silicate melts formed bypartial melting of peridotite. Amphibole (pargasitic hornblende) is a hypersolidus mineralin all compositions, although its P/T stability field dependson bulk rock chemistry. The upper pressure stability of amphiboleis marked by the appearance of garnet. The vapor-saturated (H₂O) liquidus curve for one peridotiteis between 1250? and 1300?C between 10 and 30 kb. Olivine, spinel,and orthopyroxene are either liquidus phases or co-exist immediatelybelow the temperature of the peridotite liquidus. The data suggest considerable mineralogical heterogeneity inthe oceanic upper mantle because the oceanic geotherm passesthrough the P/T band covering the appearance of garnet in variousperidotites. The variable depth to the low-velocity zone is explained byvariable aHjo conditions in the upper mantle and possibly alsoby variations in the composition of the peridotite itself. Itis suggested that komatiite in Precambrian terrane could formby direct melting of hydrous peridotite. Such melting requiresabout 1250?C compared with 1600?C which is required for drymelting. The genesis of kimberlite can be related to partial meltingof peridotite under conditions of X_H2O^v = 0.5–0.25 (X_CO2^v= 0.5–0.75). Such activities of H₂O result in meltingat depths ranging between 125 and 175 km in the mantle. Thisrange is within the minimum depth generally accepted for theformation of kimberlite.     

Crystallization of Chromite and Chromium Solubility in Basaltic Melts

The equilibrium between chromite and melt has been determinedon four basalts at temperatures of 1200–1400?C over arange of oxygen fugacity (f_o2) and pressures of 1 atm and 10kb. The Cr content of chromite-saturated melts at 1300?C and1 atm ranges from 0?05 wt.% Cr₂O₃ at a log f_o2= –3 to1?4 wt.% at a log f_o2=–12?8. The Cr²⁺/Cr³⁺ of melt increaseswith decreasing f_o2 and is estimated by assuming a constantpartitioning of Cr³⁺ between chromite and melt at constant temperature.The estimated values of Cr²⁺/Cr³⁺ in the melt are at f_o2 valuesof 4–5 orders of magnitude lower than the equivalent Fe²⁺/Fe³⁺values. The Cr/(Cr+Al) of chromite coexisting with melt at constanttemperature changes little with variation of f_o2 below log f_o2=–6.Five experiments at 10 kb indicate that Cr₂O₃ dissolved in themelt is slightly higher and the Cr/(Cr + Al) of coexisting chromiteis slightly lower than experiments at 1 atm pressure. Thus variationin total pressure cannot explain the large variations of Cr/(Cr+ Al) that are common to mid-ocean ridge basalt (MORB) chromite. Experiments on a MORB at 1 atm at f_o2 values close to fayalite-magnetite-quartz(FMQ) buffer showed that the Al₂O₃ content of melt is highlysensitive to the crystallization or melting of plagioclase,and consequently coexisting chromite shows a large change inCr/(Cr + Al). It would appear, therefore, that mixing of a MORBmagma containing plagioclase with a hotter MORB magma undersaturatedin plagioclase may give rise to the large range of Cr/(Cr +Al) observed in some MORB chromite.     

The Distribution of H2O between Cordierite and Granitic Melt: H2O Incorporation in Cordierite and its Application to High-grade Metamorphism and Crustal Anatexis

Experiments defining the distribution of H₂O [D_w = wt % H₂O(melt)/wt% H₂O(crd)]) between granitic melt and coexisting cordieriteover a range of melt H₂O contents from saturated (i.e. coexistingcordierite + melt + vapour) to highly undersaturated (cordierite+ melt) have been conducted at 3–7 kbar and 800–1000°C.H₂O contents in cordierites and granitic melts were determinedusing secondary ion mass spectrometry (SIMS). For H₂O vapour-saturatedconditions D_w ranges from 4·3 to 7 and increases withrising temperature. When the system is volatile undersaturatedD_w decreases to minimum values of 2·6–5·0at moderate to low cordierite H₂O contents (0·6–1·1wt %). At very low aH₂O, cordierite contains less than 0·2–0·3wt % H₂O and D_w increases sharply. The D_w results are consistentwith melt H₂O solubility models in which aH₂O is proportionalto X_w² (where X_w is the mole fraction of H₂O in eight-oxygenunit melt) at X_w     

Mineral Chemistry and Metasomatic Growth of Aluminous Enclaves in Gedrite--Cordierite-Gneiss from Southwestern New Hampshire, USA

The aluminous enclaves occur in gedrite-cordierite-gneissesof the Middle Ordovician Ammonoosuc Volcanics, and are composedof combinations of the aluminous minerals sillimanite (Sill),kyanite, corundum (Cor), staurolite (St), sapphirine (Sa), andspinel (Sp), which are set in a matrix of cordierite (Crd) orplagioclase (Plag). Generally, where plagioclase is present,both it and the aluminous minerals are separated from gedrite(Ged) and rare hornblende (Hbl) by cordierite. The enclavesarc interpreted to have formed near the peak of Acadian (Devonian)metamorphism at sillimanite-staurolite-muscovite grade by reactionsthat were encountered during the pressure decrease which accompaniedthe rise of gneiss domes in the region. The enclaves are divided into two main types: (1) enclaves ofcordierite surrounding aluminous minerals; and (2) enclavesof cordierite and plagioclase surrounding aluminuous minerals.Sapphirine grains contain between 9?2 and 9?3 Al atoms per formulacalculated to 14 cations. Staurolites from the enclaves areMg-rich and have (Fe²⁺+ Mn)/(Fe²⁺+Mn+Mg) ratios of 0-59–0?64. The textures and mineralogy of the enclaves suggest that theserocks originally consisted of Ged+Sill?Qz?Hbl?Sp?Plag. Theseminerals reacted to form Crd+Aluminous Minerals?Plag. The mineralogyof both main types of enclaves can be explained by two analogoussets of continuous Fe-Mg reactions:The structure of the enclavessuggests that the mineral growth by the above reactions wasdiffusion controlled, which would have resulted from oversteppingthe above reactions (i.e. the P change exceeded the reactionrate). Therefore, chemical potential gradients (relative mobilityof diffusing components) between gedrite and sillimanite controlledthe location of mineral growth. The Fe-Mg ratio of the bulkcomposition and the proportions of non-Fe-Mg minerals (quartzand sillimanite) appear to determine which continuous Fe-Mgreactions were encountered. Examples of mineral sequences in the cordierite enclaves are:Sill (core)/St+Crd/Ged (matrix); Cor+Crd (core)/Ged (matrix),and Sill (core)/St+Crd/Sa+Crd/Ged (matrix). Examples of themineral sequences in the cordierite-plagioclase enclaves are:Sill (core)/St+Plag/Plag+Crd/Hbl+Ged (matrix); Cor+Plag (core)/St+Plag/Sa+Plag/Ged+ Hbl (matrix); and St+Plag (core)/Plag+Crd/Ged+Hbl (matrix). P–µ_FeMg–1 diagrams proved to be an importanttool for understanding and illustrating the development of theenclaves. These diagrams allow one to view simultaneously allthe discontinuous and continuous Fe-Mg reactions along a P–µ_H2O(or T) rock path. With this information it is possible to determinequalitatively which reactions and what sequence of reactionsmight be encountered by bulk compositions with variable Fe-Mgratios and modal proportions of phases.     

Chemistry of Kornerupine and Associated Minerals, a Wet Chemical, Ion Microprobe, and X-Ray Study Emphasizing Li, Be, B and F Contents

Kornerupine and associated minerals in 31 samples of high-graderocks relatively rich in Al and Mg were analysed by wet chemistry,ion microprobe mass analyser, electron microprobe and X-raypowder diffraction. For 11 samples of kornerupine and threesamples of biotite (F only) analysed by both wet chemical andion microprobe methods, the best agreement was obtained forB₂O₃, whereas the ion microprobe Li₂O values were systematicallysomewhat higher than the wet chemical values. The wet chemicalmethods give Li₂O=0–0?19 wt.%; BeO=0–0?032 wt.%;B₂O₃=0–4?01 wt.%; and F=0?07–0?77 wt.% in kornerupine,whereas ion microprobe analyses on other kornerupines give valuesup to 0?35 wt.% Li₂O, O066 wt.% BeO, and 4?72 wt.% B₂O₃. Thesum B+Al+Fe³⁺+Cr is close to 6?9 atoms per 22 (O, OH, F) or21?5 (O) in kornerupine. In general, Li/Fe ratios decrease as follows: kornerupine ?sapphirinebiotite> Crd (Na<0?03 per 18 oxygens)>tourmaline, garnet,orthopyroxene. However, for cordierite with Na>004, Li/Fedecreases as follows: cordierite>kornerupine. Sapphirineand sillimanite are the only associated minerals to incorporatesignificant boron (0?1–0?85 wt.% B₂O₃) and then only whenthe single site for B in kornerupine is approaching capacity.Sillimanite B₂O₃ contents increase regularly with kornerupineF. Fractionation of fluorine increases as follows: kornerupine<biotite<tourmaline,and K^krn-BtD=(F/OH)^Krn/(F/(OH)^Bt (assuming ideal anion composition)increases with biotite Ti. Kornerupine B₂O₃ content is a measureof B₂O₃ activity in associated metamorphic fluid, whereas sillimaniteB₂O₃ content increases with temperature, exceeding 0?4 wt.%whenT=900?C at very low water activities. New data on 11 kornerupines and literature data indicate thatthe unit cell parameters a, c, and V decrease with increasingB content and b, c, and V increase with increasing Fe³⁺ content.In Fe³⁺-poor kornerupines, b increases with Mg and with (Mg+ Fe²⁺) but the effect of Mg on b via the substitution ^VIMg+^IVSi=^VIAl+^IVAloverwhelms the effect of Fe²⁺=Mg substitution.     

Formation of Wollastonite by Chemically Reactive Fluid Flow During Contact Metamorphism, Mt. Morrison Pendant, Sierra Nevada, California, USA

Quartz–calcite sandstones experienced the reaction calcite+ quartz = wollastonite + CO₂ during prograde contact metamorphismat P = 1500 bars and T = 560°C. Rocks were in equilibriumduring reaction with a CO₂–H₂O fluid with XCO₂ = 0·14.The transition from calcite-bearing, wollastonite-free to wollastonite-bearing,calcite-free rocks across the wollastonite isograd is only severalmillimeters wide. The wollastonite-forming reaction was drivenby infiltration of quartz–calcite sandstone by chemicallyreactive H₂O-rich fluids, and the distribution of wollastonitedirectly images the flow paths of reactive fluids during metamorphism.The mapped distribution of wollastonite and modeling of an O-isotopeprofile across a lithologic contact indicate that the principaldirection of flow was layer-parallel, directed upward, withany cross-layer component of flow <0·1% of the layer-parallelcomponent. Fluid flow was channeled at a scale of 1–100m by pre-metamorphic dikes, thrust and strike-slip faults, foldhinges, bedding, and stratigraphic contacts. Limits on the amountof fluid, based on minimum and maximum estimates for the displacementof the wollastonite reaction front from the fluid source, are(0·7–1·9) x 10⁵ cm³ fluid/cm² rock. Thesharpness of the wollastonite isograd, the consistency of mineralthermobarometry, the uniform measured ¹⁸O–¹⁶O fractionationsbetween quartz and calcite, and model calculations all arguefor a close approach to local mineral–fluid equilibriumduring the wollastonite-forming reaction. KEY WORDS: contact metamorphism, fluid flow, wollastonite, oxygen isotopes, reaction front     

Crystallization Pressure and Cooling History of the Giles Layered Igneous Complex, Central Australia

The Giles Complex, central Australia, consists of a series oflarge layered gabbroic/ultramafic intrusions emplaced in acidicand intermediate granulites of the Middle Proterozoic Musgraveblock. Lithologies range from well-layered dunite, wehrlite,and pyroxenite in the lower primitive series, to massive olivinegabbro, gabbronorite, and anorthosite in the main units, andferrodiorites, vanadife-rous magnetite layers, and granophyresin the upper, most fractionated parts. Unlike many layered intrusions,the Giles Complex is tectonically dismembered to an extent thata reconstruction of the original morphology is difficult. The Complex is believed to be a type example for medium- tohigh-pressure differentiation. (1) Chilled margin samples (wherepreserved) are orthopyroxene-phyric, and liquidus olivine isreplaced by liquidus orthopyroxene at an mg-number of 0.77,suggesting a pressure-related expansion of the orthopyroxenestability field (Goode & Moore, 1975). (2) Tschermaks substitutioninto pyroxene and plagioclase-orthoclase solid solution areextensive, indicating unusually high crystallization temperaturerelated to high pressure; antiperthites in the Giles Complexare amongst the most calcic reported for terrestrial rocks.(3) The lower primitive cumulate units of the Complex are coroniticand feature a variety of subsolidus high-pressure reaction textures;olivine and cumulus chromite have reacted with calcic plagioclaseto orthopyroxene-clinopyroxene-spinel, olivine-spinel, and clinopyroxene-spinelsymplectites. The principal reaction mechanism for the symplectites was continuousmass transfer of alumina from plagioclase toward spinel, asthe Complex passed from the olivine-plagioclase stability fieldinto the pyroxene-spinel field during cooling. Geothermometersapplicable to the cumulates record a wide range of equilibrationtemperatures from late-magmatic to granulite-metamorphic conditions.FeMg₁ exchange gives closure temperatures around 600–700?C,whereas Al₂Mg₁Si₁ net-transfer equilibria have preserved highertemperatures around 750–900 ?C. Defocused beam bulk analysesof exsolved cumulus clinopyroxenes and intercumulus plagioclasesrecover magmatic compositions; i. e., two-pyroxene solvus CaMg_-1temperatures plot around 1120?50?C, whereas two-feldspar thermometersgive 1200?C. Pressures are calculated from thermochemical data with the heterogeneousequilibria 2 fo + an = en + di + sp, fo + an = di + Mg-Ts, andfo + an = en + Ca-Ts, after correcting spinel activities forselective retrograde FeMg_-1 exchange during cooling. These equilibria,combined with orthopyroxene-spinel Al₂Mg_-1Si_-1 temperaturesfor metamorphic assemblages and two-pyroxene temperatures forcumulus phases define a medium-pressure cooling path extendingfrom 1150 ?C (at 6?5 kb) to 750 ?C (at 6?2 kb). The resultssuggest an isobaric cooling path for the Giles Complex, withno evidence for a post-intrusive metamorphic overprint. Themagmas intruded at lower to middle crustal levels after thepervasive deformation in the Musgrave block, and probably afterthe peak metamorphic event.     

Stability and Phase Relations of Trioctahedral Calcium Brittle Micas (Clintonite Group)

On the pseudobinary join CaO:3MgO:Al₂O₃:2SiO₂:_xH2O–CaO:1.25MgO:2.75 Al₂O₃: 0.25SiO₂:_xH₂O clintonite mixed crystals Ca(Mg_{1+ x}Al_{2 – x}) (Al_{4 – x}Si_xO₁₀)(OH)₂ with x rangingfrom 0.6 to 1.4 occur in the temperature range 600–830?C, 2 kb fluid pressure. On the MgSirich side clintonites coexistwith chlorite, forsterite, diopside, and calcite (due to smallamounts of CO₂ in the gas phase) and, at lower temperatures,also with idocrase, hydrogrossularite, and aluminous serpentine.Decomposition of clintonite over a divariant temperature rangeoccurs above 830 ?C, 2 kb; clintonite-free subsolidus assemblagescomprising three or four solid phases are formed in the temperatureranges 890 ?–1120 ?C. The subsolidus assemblages can berepresented in a polyhedron defined by the corners forsterite,diopside, melilite, spinel, anorthite, corundum, and calciumdialuminate. Above 1120 ?C partial melting occurs. The upper thermal stability limits of three selected compositionshave been reversed in the P-T range 0.5–20 kb and 730–1050 ?C, respectively. Below some 4 kb breakdown is dueto the divariant reactions: (1)Ca(Mg_2.25Al_0.75)(Al_2.75)(Si_1.25O₁₀)(OH)₂ spinel+diopside_ss+forsterite+clintonite_ss+vapor, (2)Ca(Mg₂Al)(Al₃SiO₁₀)(OH)₂ spinelx002B;melilite_ss+anorthite+clintonite_ss+vapor, (3)Ca(Mg_1.75Al_1.25)(Al_3.25)(Si_0.75O₁₀)(OH)₂ spinel+melilite_ss+corundum+clintonite_ss+vapor, At the terminations of the divariant temperature ranges (1)melilite_ss, (2) diopside_ss, and (3) anorthite enter those assemblagesand clintonitess disappears completely. The reactions can berepresented by the following equations (1)log,_H2O = 10.2879–8113/T+0.0856(P–1)/T, (2)log = 9.5852–7325/T+0.0794(P–1)/T, (3)log = 7.8358–5250/T+0.077(P–1)/T, with P expressed in bars and Tin ?K. Above 4 kb the upper thermalstability limit of clintonite is defined by incongruent melting,with grossularite participating at pressures above 9 kb. Thesecurves exhibit a very steep, probably even negative slope inthe P-T diagram. There is a close correspondence between natural clintonite-bearingassemblages and thosefound experimentally. The rarity of clintonitein nature is not due to special conditions of pressure and temperaturebut rather due to special bulk compositions of the rocks.     

An Experimental Study of Water and Carbon Dioxide Solubilities in Mid-Ocean Ridge Basaltic Liquids. Part I: Calibration and Solubility Models

Experiments were conducted to determine the solubilities ofH₂O and CO₂ and the nature of their mixing behavior in basalticliquid at pressures and temperature relevant to seqfloor eruption.Mid-ocean ridge basaltic (MORB) liquid was equilibrated at 1200°Cwith pure H₂O at pressures of 176–717 bar and H₂O—CO₂vapor at pressures up to 980 bar. Concentrations and speciationof H₂O and CO₂ dissolved in the quenched glasses were measuredusing IR spectroscopy. Molar absorptivities for the 4500 cm^–1band of hydroxyl groups and the 5200 and 1630 cm^–1 bandsof molecular water are 0•67±0•03, 0•62±0•07,and 25±3 l/mol-cm, respectively. These and previouslydetermined molar absorptivities for a range of silicate meltcompositions correlate positively and linearly with the concentrationof tetrahedral cations (Si+Al). The speciation of water in glass quenched from vapor-saturatedbasaltic melt is similar to that determined by Silver &Stolper (Journal of Petrology 30, 667–709, 1989) in albiticglass and can be fitted by their regular ternary solution modelusing the coefficients for albitic glasses. Concentrations ofmolecular water measured in the quenched basaltic glasses areproportional to f H₂O in all samples regardless of the compositionof the vapor, demonstrating that the activity of molecular waterin basaltic melts follows Henry's law at these pressures. Abest fit to our data and existing higher-pressure water solubilitydata (Khitarov et al., Geochemistry 5, 479–492, 1959;Hamilton et al., Journal of Petrology 5, 21–39, 1964),assuming Henrian behavior for molecular water and that the dependenceof molecular water content on total water content can be describedby the regular solution model, gives estimates for the V^{o, m}_H2Oof 12±1 cm³/mol and for the 1-bar water solubility of0•11 wt%. Concentrations of CO² dissolved as carbonate in the melt forpure CO₂-saturated and mixed H₂O-CO₂-saturated experiments area simple function of f_CO2 These results suggest Henrian behaviorfor the activity of carbonate in basaltic melt and do not supportthe widely held view that water significantly enhances the solutionof carbon dioxide in basaltic melts. Using a V^{o, m}_r of 23 cm³/mol(Pan et al., Geochimica et Cosmochimica Acta 55, 1587–1595,1991), the solubility of carbonate in the melt at 1 bar and1200°C is 0•5 p.p.m. Our revised determination of CO₂solubility is 20% higher than that reported by Stolper &Holloway (Earth and Planetary Science Letters 87, 397–408,1988). KEY WORDS: mid-ocean ridge basalts; water and carbon dioxide solubility; experimental petrology     

Peralkalinity, Al{rightleftharpoons}Si Substitution, and Solubility Mechanisms of H2O in Aluminosilicate Melts

The solubility mechanisms of H₂O in peralkaline sodium aluminosilicatequenched melts (anhydrous NBO/T = 0.5) have been studied withRaman spectroscopy as a function of Al/(Al + Si) (0–0–3)and H²O content (0–7.5 wt.%). The coexisting structuralunits in the anhydrous quenched melts are TO2 (Q4), T2O5(Q3),and TO3 (Q2). In Al-free Na₂Si₄O₉ (NS4) melt, H₂O forms complexes with Na⁺(Na–OH bonds) and with Si⁴⁺ (Si–OH bonds). MolecularH₂O is also detected. TO3 structural units are not detectedin this composition. In the H₂O concentration range between0 and 4 wt.%, there is an approximately 20% increase in NBO/Tresulting from the increased abundance ratio, T₂O₅/TO2. Withfurther increments in water activity, the NBO/T of hydrous NS4melt is reduced. The depolymerization results from hydroxylationof the silica tetrahedra, whereas polymerization is due to formationof complexes with Na–OH bonding. In Al-bearing compositions on the Na₂Si₄O₉–Na₂(NaAl)₄O₉–join, there is evidence for Al–OH bonding in additionto Na–OH and Si–OH bonds. Among these complexes,the relative abundance of those with Si–OH bonds diminisheswith increasing Al/(A1 + Si), whereas complexes with Al–OHand Na–OH bonds become more important. Complexes withNa–OH bonds dominate for H₂O4 wt.%, whereas complexeswith Al–OH dominate at higher water content. The threestructural units, TO₃, T₂O₅, and TO², were observed in bothanhydrous and hydrous peralkaline sodium aluminosilicate melts.Their abundance varies, however, with the H₂O concentrationin the melts. The NBO/T decreases to a minimum (a 30–50%lowering of NBO/T relative to anhydrous materials) for low H₂Ocontents (3–4 wt.% H₂O), and increases as the H₂O contentis increased further.     

Fluid Flow During Contact Metamorphism of Ophicarbonate Rocks in the Bergell Aureole, Val Malenco, Italian Alps

Contact-mctamorphic assemblages in ophicarbonate from the Bergellaureole correspond either to model isobaric invariant T-XCO₂points [Atg-Cal-Di-Tr-Fo (6 samples) and Atg-Cal-Tr-Fo-Dol (2)]or to isobaric univariant T-XCO₂, curves [Tr-Cal-Di-Atg (18),Tr-Dol-Atg-Cal (1), Atg-Cal-Fo-Di (1), and Atg-Cal-Tr-Fo (1)].Calcite-dolomite thermometry and mineral-fluid equilibria inthe invariant assemblages record T=440–540C at P=3•5kbar. Equilibrium metamorphic fluids were very H₂O rich withX CO₂,=0•001–0•027. In the invariant assemblagesTr + Fo were produced by prograde decarbonation-dehydrationreactions. In contrast, measured modes and reaction texturesin samples with univariant assemblages indicate thai Tr wasproduced by carbonation reactions. The apparent paradox of simultaneousdecarbonation reactions in the model isobaric invariant assemblagesand carbonation reactions in univariant assemblages is resolvedby local mineral-fluid equilibrium and fluid flow through ophicarbohatesin the direction of decreasing temperature as the aureole heated.Time-integrated flux (q) was computed from measured reactionprogress in 28 samples for models of both horizontal and verticaldown-temperature flow. Results are similar, with q decreasingrapidly from (0•2–5•1) 10⁵ cm³ fluid/cm² rock1•3–1•7 km from the intrusion to 0–0•610⁵cm³/cm² at 1•8–4•0 km. The decrease in q ismore consistent with vertical than horizontal flow. Variationsin time-integrated flux of more than an order of magnitude arerecorded by samples from the same outcrop. The absence of carbonatein adjacent metaperidotite indicates that flow was confinedto the ophicarbonate. Channelized, spatially heterogeneous,vertical flow can be explained by the brecciation and strongvertical foliation of the ophicarbonate relative to surroundingmassive metaperidotite. Generation of metamorphicfluids by decarbonation-dehydrationreactions within the ophicarbonates explains larger averageflux 1–2 km from the intrusion compared with more distalpoints. KEY WORDS: Bergell; contact metamorphism; fluid flow; ophicarbonate ^*Telephone: (410) 516-8121. Fax: (410) 516-7933     

Petrogenesis of the Eastern Bushveld Complex: Crystallization of the Middle Critical Zone

The bronzite—chromite-anorthite assemblage of the F—unit(Cameron & Emerson, 1959) from the Critical Zone of theBushveld Igneous Complex, was examined with the aid of an electrolyticcell designed after Sato (1971). The resultant fO₂-T data reveala last equilibration at an fO₂ value of 10^{11·82 ±·40} atm and at a temperature of 1091 ± 35 °C.These fO₂-T data when compared with: (1) a one atmosphere quenching—technique solidus determinationof 1110 ± 5 °C, (2) the Bushveld plagioclase compositional trends (Cameron,1970), (3) Bushveld petrofabric examinations (Cameron, 1969) (4) phase equilibria in the system CaO–MgO–FeO–CaAl₂Si₂O₈–SiO₂(Roeder & Osborn, 1966), (5) phase equilibria in the system CaAl₂Si₂O₈–NaAlSi₃O₈–SiO₂–MgO–Fe–O₂–H₂O–CO₂(Eggler, 1974), all support the idea that the Eastern Bushveld magma was notappreciably differentiating in the middle Critical Zone betweenF and the L Horizons, an accumulation of nearly 220 meters.     

The Stability of Andradite, Hedenbergite, and Related Minerals in the System Ca--Fe--Si--O--H

Phase relations for the bulk compositions 3CaO·2FeO_x·3SiO₂+excessH₂O and CaO·FeO_x·2SiO₂+excess H₂O were determinedusing conventional hydrothermal techniques with solid phaseoxygen buffers to control fO₂. Andradite, Ca₃Fe³⁺₂Si₃O₁₂, synthesized above 550 °C hasan average unit cell edge, a_o, of 12.055±0.001 Å,and an index of refraction, n, of 1.887±0.003. Belowthis temperature, a_o increases whereas n decreases, indicatingthe formation of a member of the andradite-hydroandradite solidsolution. At 2000 bars P_fluid andradite is stable above an f_O2of 10¹⁵ bar at 800 °C and 10-³² bar at 400 °C. At lowerf_O2 andradite+fluid gives way at successively lower temperaturesto the condensed assemblages magnetite+wollastonite, kirschsteinite(CaFe²⁺SiO₄)+ wollastonite and kirschsteinite+xonotlite (Ca₆Si₆O₁₇(OH)₂). Synthetic hedenbergite, CaFe²⁺Si₂O₆, has average unit cell dimensionsof a_o = 9.857± 0.004 Å, b_o = 9.033±0.002Å, c_o = 5.254±0.002 Å and ß = 104.82°±0.03°,and refractive indices of n = 1.731±0.003 and n = 1.755±0.005.At 2000 bars P_fiuid, hedenbergite is stable below an f_O2 of10-¹³ bar at 800 °C and 10-²⁸ bar at 400 °C. Above thesef_O2 values, hedenbergite+O₂ breaks down to andradite+magnetite+quartz. The mineral pair andradite +hedenbergite thus limit the f_O2range possible for their joint formation under equilibrium conditions. The hydration of wollastonite to xonotlite occurs at much lowertemperatures than previous experimental work indicated. A tentativehigh temperature limit for this reaction is set at 185°±15°C and 5000±25 bars and 210°±15 °Cand 2000±20 bars. Inasmuch as the growth of xonotlitefrom wollastonite + H₂O was never accomplished, this high temperaturelimit does not represent an equilibrium univariant curve. Nine phases were encountered in the study of andradite and hedenbergite.They are andradite, hedenbergite, magnetite, wollastonite, kirschsteinite,xonotlite, quartz, ilvaite, and vapor (fluid). An invariantpoint analysis using the method of Schreinemakers shows thetopologic relations of the reactions involved. The resultinggrid can be used to interpret natural occurrences.     

Melting and Thermal Reconstitution of Pelitic Xenoliths, Wehr Volcano, East Eifel, West Germany

Pelitic xenoliths derived from amphibolite grade basement rocksoccur within a Pleistocene, trachytic, pyroclastic unit of theWehr volcano, East Eifel, West Germany: With increasing temperatureand/or prolonged heating at high temperature, quartz-plagioclaseand micaceous layers of the xenoliths have undergone meltingto form buchites and thermal reconstitution by dehydration reactions,melting and crystallization to form restites respectively. Thexenoliths provide detailed evidence of melting, high temperaturedecomposition of minerals, nucleation and growth of new phasesand P-T-f_o2 conditions of contact metamorphism of basement rocksby the Wehr magma. Melting begins at quartz-oligoclase (An_17·3Ab_82·3Or_0·4-An_20·0Ab_78·1Or_1·9)grain boundaries in quartz-plagioclase rich layers and the amountof melting is controlled by H₂O and alkalis released duringdehydroxylation/oxidation of associated micas. Initially, glasscompositions are heterogeneous, but with increasing degreesof melting they become more homogeneous and are similar to S-typegranitic minimum melts with SiO₂ between 71 and 77 wt. per cent;A/(CNK) ratios of 1·2–1·4; Na₂O < 2·95and normative corundum contents of 1·9–4·0per cent. Near micas plagioclase melts by preferential dissolutionof the NaAlSi₃O₈ component accompanied by a simultaneous increasein CaAl²Si²O⁸ (up to 20 mol. per cent An higher than the bulkplagioclase composition) at the melting edge. With increasingtemperature the end product of fractional melting is the formationand persistence of refractory bytownite (An_78–80) in thosexenoliths where extensive melting has taken place. Initial stage decomposition of muscovite involves dehydroxylation(H₂O and alkali loss). At higher temperatures muscovite breaksdown to mullite, sillimanite, corundum, sanidine and a peraluminousmelt. Mullite (40–43 mol. per cent SiO₂) and sillimanite(49 mol. per cent SiO₂) are Fe₂O₃ and TiO₂ rich (up to 6·1–0·84and 3·6–0·24 wt. per cent respectively).Al-rich mullite (up to 77 wt. per cent Al₂O₃) occurs with corundumwhich has high Fe₂O₃ and TiO₂ (up to 6·9 and 2·1wt. per cent respectively). Annealing at high temperatures andreducing conditions results in the exsolution of mullite fromsillimanite and ilmenite from corundum. Glass resulting fromthe melting of muscovite in the presence of quartz is peraluminous(A/(CNK) = 1·3) with SiO² contents of 66–69 percent and normative corundum of 4 per cent. Sanidine (An_1·9Ab_26·0Or_72·1-An_1·3Ab_15·9Or_82·9)crystallized from the melt. Dehydroxylation and oxidation of biotite results in a decreaseof K₂O from 8·6 to less than 1 wt. per cent and oxidetotals (less H₂O + contents) from 96·5 to 88·6,exsolution of Al-magnetite, and a decrease in the Fe/(Fe + Mg)ratio from 0·41 to 0·17. Partial melting of biotitein the presence of quartz/plagioclase to pleonaste, Al-Ti magnetite,sanidine(An_2·0Ab_34·9Or63·1) and melt takesplace at higher temperatures. Glass in the vicinity of meltedbiotite is pale brown and highly peraluminous (A/CNK = 2·1)with up to 6 wt. per cent MgO+FeO_{(total iroq)} and up to 10 percent normative corundum. Near liquidus biotite with higher Al₂O₃and TiO₂ than partially melted biotite crystallized from themelt. Ti-rich biotites (up to 6 wt. per cent TiO₂) occur withinthe restite layers of thermally reconstituted xenoliths. Meltingof Ti-rich biotite and sillimanite in contact with the siliceousmelt of the buchite parts of xenoliths resulted in the formationof cordierite (100 Mg/(Mg+Fe+Mn) = 76·5–69·4),Al-Ti magnetite and sanidine, and development of cordierite/quartzintergrowths into the buchite melt. Growth of sanidine enclosedrelic Ca-plagioclase to form patchy intergrowths in the restitelayers. Cordierite (100 Mg/(Mg+Fe+Mn) = 64–69), quartz,sillimanite, mullite, magnetite and ilmenite, crystallized fromthe peraluminous buchite melt. Green-brown spinels of the pleonaste-magnetite series have awide compositional variation of (mol. per cent) FeAl₂O₄—66·6–45·0;MgAl₂O₄—53·0–18·7; Fe₃O₄—6·9–28·1;MnAl₂O₄—1·2–1·5; Fe₂TiO₄—0·6–6·2.Rims are generally enriched in the Fe₃O₄ component as a resultof oxidation. Compositions of ilmenite and magnetite (single,homogeneous and composite grains) are highly variable and resultfrom varying degrees of high temperature oxidation that is associatedwith dehydroxylation of micas and melting. Oxidation mainlyresults in increasing Fe³⁺, Al and decreasing Ti⁴⁺, Fe²⁺ inilmenite, and increasing Fe²⁺, Ti⁴⁺ and decreasing Fe³⁺ in associatedmagnetite. A higher degree of oxidation is reached with exsolutionof rutile from ilmenite and formation of titanhematite and withexsolution of pleonaste from magnetite. Ti-Al rich magnetite(5·1–7·5 and 8·5–13·5wt. per cent respectively) and ilmenite crystallized from meltsin buchitic parts of the xenoliths. Chemical and mineralogic evidence indicates that even with extensivemelting the primary compositions of individual layers in thexenoliths remained unmodified. Apparently the xenoliths didnot remain long enough at high temperatures for desilicationand enrichment in Al₂O₃, TiO₂, FeO, Fe₂O₃, and MgO that resultsby removal of a ‘granitic’ melt, and/or by interactionwith the magma, to occur. T °C-f_o2 values calculated from unoxidized magnetite/ilmenitegive temperatures ranging from 615–710°C for contactmetamorphism and the beginning of melting, and between 873 and1054°C for the crystallization of oxides and mullite/sillimanitefrom high temperature peraluminous melts. f_o2 values of metamorphismand melting were between the Ni-NiO and Fe₂O₃-Fe₃O₄ buffer curves.The relative abundance of xenolith types, geophysical evidenceand contact metamorphic mineralogy indicates that the xenolithswere derived from depths corresponding to between 2–3kb P_load = P_fluid. The xenoliths were erupted during the latestphreatomagmatic eruption from the Wehr volcano which resultedin vesiculation of melts in partially molten xenoliths causingfragmentation and disorientation of solid restite layers.     

The Solubility of Alumina in Orthopyroxene Coexisting with Garnet in FeO-MgO--Al2O3--SiO2 and CaO--FeO--MgO--Al2O3--SiO2

The pressure-temperature-compositional (P-T-X) dependence ofthe solubility of Al₂O₃ in orthopyroxene coexisting with garnethas been experimentally determined in the P-T range 5–30kilobars and 800–1200 ?C in the system FeO—MgO—Al₂O₃—SiO₂(FMAS). These results have been extended into the CaO—FeO—MgO—Al₂O₃—SiO₂(CFMAS) system in a further set of experiments designed to determinethe effect of the calcium content of garnet on the Al₂O₃ contentsof coexisting orthopyroxene at near-constant Mg/(Mg + Fe). Startingmaterials were mainly glasses of differing Mg/(Mg + Fe) or Ca/(Ca+ Mg + Fe) values, seeded with garnet and orthopyroxene of knowncomposition, but mineral mixes were also used to demonstratereversible equilibrium. Experiments were performed in a piston-cylinderapparatus using a talc/pyrex medium. Measured orthopyroxene and corrected garnet compositions werefitted by multiple and stepwise regression techniques to anequilibrium relation in the FMAS system, yielding best-fit,model-dependent parameters G^o_y= –5436 + 2.45T cal mol^–1,and W^M1_FeA1= –920 cal mol^–1. The volume change ofreaction, V^o, the entropy change, S^o₉₇₀ and the enthalpy changeH^o_1,970, were calculated from the MAS system data of Perkinset al. (1981) and available heat capacity data for the phases.Data from CFMAS experiments were fitted to an expanded equilibriumrelation to give an estimate of the term W^ga_CaMg = 1900 ? 400cal/mole cation, using the other parametric values already obtainedin FMAS. The experimental data allow the development of a arnet-orthopyroxenegeobarometer applicable in FMAS and CFMAS: where This geobarometer is applicable to both pelitic and metabasicgranulites containing garnet orthopyroxene, and to garnet peridoditeand garnet pyroxenite assemblages found as xenoliths in diatremesor in peridotite massifs. It is limited, however, by the necessityof an independent temperature estimate, by errors associatedwith analysis of low Al₂O₃ contents in orthopyroxenes in high-pressureor low-temperature parageneses, and by uncertainties in thecomposition of garnet in equilibrium with orthopyroxene. Ananalysis of errors associated with this formulation of the geobarometersuggests that it is subject to great uncertainty at low pressuresand for Fe-rich compositions. The results of application ofthis geobarometer to natural assemblages are presented in acompanion paper.